Abstract
The effect of solvent polarity on the observed hyperfine coupling constants of nitroxide radicals has been investigated both in the presence of and in the absence of hydrogen donors. With inert solvents, the observed hyperfine coupling constant increases linearly with (ϵ - ̊ 1)/(ϵ + 1). With hydrogen donors, the observed hyperfine coupling constants are much greater, in part because of the dielectric constant of the medium and in part because of the equilibrium between free and complexed radicals. Correcting for the effect of the dielectric constant of the medium on the observed hyperfine coupling constants in the determination of association constants of transient complexes is illustrated for the donors C 3H 7OH, C 4H 9OH, CF 3CH 2OH, C 6H 5OH, (CH 3) 3COH, and CHCl 3. Association constants for these donors with TMPO at room temperature in benzene are found to be in the range from 0.68 to 2.04 M −1.
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